CN112920509A - Antibacterial polypropylene composite material and preparation method thereof - Google Patents
Antibacterial polypropylene composite material and preparation method thereof Download PDFInfo
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- CN112920509A CN112920509A CN202110136574.1A CN202110136574A CN112920509A CN 112920509 A CN112920509 A CN 112920509A CN 202110136574 A CN202110136574 A CN 202110136574A CN 112920509 A CN112920509 A CN 112920509A
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- -1 polypropylene Polymers 0.000 title claims abstract description 84
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 80
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 80
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011787 zinc oxide Substances 0.000 claims abstract description 45
- 239000000945 filler Substances 0.000 claims abstract description 44
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 229910000085 borane Inorganic materials 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 238000002715 modification method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 27
- 238000004898 kneading Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920001903 high density polyethylene Polymers 0.000 claims description 12
- 239000004700 high-density polyethylene Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 230000000845 anti-microbial effect Effects 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 229920001684 low density polyethylene Polymers 0.000 claims description 6
- 239000004702 low-density polyethylene Substances 0.000 claims description 6
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000003242 anti bacterial agent Substances 0.000 abstract description 19
- 230000002045 lasting effect Effects 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 description 16
- 239000004033 plastic Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses an antibacterial polypropylene composite material, which comprises the following components in percentage by mass: 35-90% of polypropylene, 0-10% of polyethylene, 5-30% of filler, 0.3-10% of doped nano zinc oxide, 0.2-5% of borane coupling agent, 0-10% of toughening agent and 0-2% of processing aid; the filler is a modified filler prepared by a coating modification method, and the surface of the filler is coated with an inorganic coating layer; the doped nano zinc oxide is silver-doped nano zinc oxide. The antibacterial agent in the antibacterial polypropylene composite material has good dispersibility and compatibility in polypropylene, the composite material has good antibacterial effect and lasting antibacterial performance, and the composite material has high strength and good toughness.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antibacterial polypropylene composite material and a preparation method thereof.
Background
The antibacterial plastic can inhibit or kill bacteria, mold, alchogen, algae and even viruses stained on the plastic. Antibacterial plastics are generally obtained by adding a small amount of an antibacterial agent to the plastic.
The antibacterial agents added to plastics are generally classified into inorganic antibacterial agents and organic antibacterial agents. Inorganic antibacterial agents are mainstream because of their good stability and wide antibacterial range. The inorganic antibacterial agent mainly comprises three major varieties of silver, zinc oxide, titanium dioxide and the like. The silver-based antibacterial agent mainly has the characteristic of high antibacterial efficiency, but is relatively expensive. The zinc oxide has a wide antibacterial spectrum and can kill or inhibit bacteria, mold and fungi. The antimicrobial effect of titanium dioxide is relatively dependent on the wavelength of light in the environment of use. Under the irradiation of ultraviolet rays, titanium dioxide has stronger antibacterial force. However, in the visible range, titanium dioxide has a relatively weak antibacterial effect. Therefore, silver and zinc oxide are widely applied to plastic antibacterial.
The dispersibility of the antibacterial agent in plastics and the compatibility of the antibacterial agent and plastics are key factors in the development of antibacterial plastics. The better the dispersion of the antimicrobial in the plastic, the less amount of plastic needs to be added to achieve an effective level of antimicrobial activity. In addition, the antibacterial plastic needs to maintain basic mechanical properties of the plastic, such as tensile property, impact property, bending property, fluidity and the like. Therefore, there is a need to improve the compatibility between the antibacterial agent and the plastic.
For zinc oxide-filled polypropylene-based antibacterial plastics, the following studies are made: the Cai Jian and the like report in the research on the antibacterial performance of the nano zinc oxide polypropylene fiber that the antibacterial performance of the nano zinc oxide in the polypropylene fiber is obviously superior to that of the micro powder zinc oxide. The preparation and performance research of polypropylene/tetrapod-like zinc oxide whisker composite material reports that tetrapod-like zinc oxide whiskers treated by different coupling agents can improve the mechanical property of the composite material. When the addition amount of the zinc oxide whisker is 4%, the antibacterial rate of the composite material on staphylococcus aureus, escherichia coli and bacillus subtilis can reach more than 50%. However, it is not reported whether the coupling agent improves the antibacterial property of the composite material. And the coupling agent is generally liquid, needs to fully wet the surface of the zinc oxide, has a slow process of generating chemical reaction with the surface of the zinc oxide, and is inconvenient for large-scale industrial production. Surface modification of zinc oxide by three methods, namely silane coupling agent, stearic acid, maleic anhydride grafted SEBS, etc., is reported in Effects of stabilizers on mechanical and inorganic properties of injected molded nano-ZnO filled polypropylene. The silane coupling agent and the stearic acid can improve the dispersibility of the zinc oxide in the polypropylene base material. Maleic anhydride grafting of SEBS causes agglomeration of the zinc oxide particles. As described above, the prior art has mainly focused on improving the dispersibility of zinc oxide in polypropylene by a silane coupling agent, stearic acid, or the like. The surface modification of the liquid coupling agent is not convenient for large-scale industrial production, and the aliphatic surface modifying agent such as stearic acid can be a nutrient source for the reproduction of partial bacteria and fungi, and is not suitable for being used as an additive of antibacterial plastics.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an antibacterial polypropylene composite material and a preparation method thereof.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
the antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 35-90% of polypropylene, 0-10% of polyethylene, 5-30% of filler, 0.3-10% of doped nano zinc oxide, 0.2-5% of borane coupling agent, 0-10% of toughening agent and 0-2% of processing aid;
the filler is a modified filler prepared by a coating modification method, and the surface of the filler is coated with an inorganic coating layer;
the doped nano zinc oxide is silver-doped nano zinc oxide.
Further, the polypropylene is one of homo-polypropylene resin and co-polypropylene resin, or a mixture of homo-polypropylene resin and co-polypropylene resin.
Further, the polyethylene is one of high density polyethylene and low density polyethylene, or a mixture of high density polyethylene and low density polyethylene.
Further, the filler is one or a mixture of two or more of talcum powder, calcium carbonate, barium sulfate, mica, wollastonite, kaolin, aluminum hydroxide and magnesium hydroxide.
Further, the inorganic coating layer on the surface of the filler is a silicon dioxide coating layer or a titanium dioxide coating layer.
Further, the toughening agent is one or a combination of two or more of ethylene-octene copolymer, ethylene-butene copolymer and ethylene-propylene rubber.
Further, the doped nano zinc oxide is prepared by adding silver nitrate and a precipitator into a zinc salt solution, reacting, washing, drying and calcining at high temperature.
Further, the processing aid includes, but is not limited to, one or a combination of two or more of an antioxidant, a lubricant, an ultraviolet absorber and a heat stabilizer.
The invention further provides a preparation method of the antibacterial polypropylene composite material, which comprises the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
Further, the double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190-200 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 210-220 ℃, and the temperature of the fourth zone is 205-215 ℃.
The invention has the beneficial effects that:
(1) the antibacterial agent in the composite material is silver-doped nano zinc oxide; according to the invention, the nano silver with small-size effect and quantum size effect is doped in the nano zinc oxide, so that the antibacterial agent has better antibacterial effect in both visible light region and ultraviolet irradiation; the nano zinc oxide is doped with silver particles, so that the antibacterial agent has a large specific surface area and very high surface activity, the contact area between the antibacterial agent and bacteria is increased, the antibacterial agent is more uniformly dispersed in a polypropylene matrix, and finally, the composite material has longer antibacterial performance, more obvious antibacterial effect, higher high temperature resistance and wide antibacterial spectrum;
(2) the filler in the composite material is a modified filler prepared by a coating modification method, and the surface of the filler is coated with an inorganic coating layer; the inorganic coating layer is used for coating the filler, so that the stability of the filler structure can be enhanced, the specific surface area is increased, the agglomeration of the filler is prevented, and the dispersibility and the fluidity of the filler are improved;
(3) the borane coupling agent in the composite material can act on the interfaces between the filler and the polypropylene and the polyethylene and between the doped nano zinc oxide and the polypropylene and the polyethylene through different reactive groups to form stronger combination and coupling, greatly improve the compatibility between the filler, the antibacterial agent and the polypropylene base material, and improve the strength and the antibacterial property of the polypropylene composite material; moreover, the borane coupling agent is not a fatty acid or salt coupling agent and cannot be used as a nutrient substance by bacteria, fungi and the like, so that a better antibacterial effect is ensured; the borane coupling agent is not a liquid coupling agent, has quicker reaction with the doped zinc oxide and the filler, has more obvious effect and is suitable for large-scale production.
The borane coupling agent, the filler and the doped zinc oxide antibacterial agent are matched, so that the dispersibility and compatibility of the filler and the antibacterial agent in polypropylene and polyethylene matrixes can be improved, the antibacterial effect with stability and durability and high antibacterial activity is realized, and the composite material is endowed with high strength and high toughness.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 35-90% of polypropylene, 0-10% of polyethylene, 5-30% of filler, 0.3-10% of doped nano zinc oxide, 0.2-5% of borane coupling agent, 0-10% of toughening agent and 0-2% of processing aid;
the filler is a modified filler prepared by a coating modification method, and the surface of the filler is coated with an inorganic coating layer;
the doped nano zinc oxide is silver-doped nano zinc oxide.
The polypropylene is one of homo-polypropylene resin and co-polypropylene resin, or a mixture of homo-polypropylene resin and co-polypropylene resin.
Wherein the polyethylene is one of high density polyethylene and low density polyethylene, or a mixture of high density polyethylene and low density polyethylene.
Wherein the filler is one or a mixture of two or more of talcum powder, calcium carbonate, barium sulfate, mica, wollastonite, kaolin, aluminum hydroxide and magnesium hydroxide.
Wherein, the inorganic coating layer on the surface of the filler is a silicon dioxide coating layer or a titanium dioxide coating layer.
Wherein, the toughening agent is one or the combination of two or more of ethylene-octene copolymer, ethylene-butene copolymer and ethylene-propylene rubber.
Wherein, the doped nano zinc oxide is prepared by adding silver nitrate and a precipitator into a zinc salt solution, reacting, washing, drying and calcining at high temperature.
Specifically, the preparation process of the doped nano zinc oxide comprises the following steps: weighing a certain amount of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in a certain amount of deionized water, weighing 1% of silver nitrate relative to the mass of the zinc nitrate hexahydrate, and dissolving the silver nitrate in a prepared zinc nitrate solution; stirring at room temperature, adding a certain amount of sodium hydroxide solution with the concentration of 0.2-1mol/L as a precipitator under the stirring condition after uniformly stirring to obtain white precipitate, sequentially washing with deionized water and absolute ethyl alcohol, drying at 75 ℃ for 4-5 hours under the vacuum condition, and calcining at 450 ℃ for 4-5 hours to obtain the silver-doped nano zinc oxide powder.
Wherein, the processing aid comprises one or the combination of two or more of an antioxidant, a lubricant, an ultraviolet absorber and a heat stabilizer.
The invention further provides a preparation method of the antibacterial polypropylene composite material, which comprises the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190-200 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 210-220 ℃, and the temperature of the fourth zone is 205-215 ℃.
Example 1
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 35% of homo-polypropylene, 10% of high-density polyethylene, 30% of calcium carbonate filler, 8% of silver-doped nano zinc oxide, 5% of borane coupling agent, 10% of ethylene-octene copolymer, 1% of antioxidant and 1% of ultraviolet absorbent; wherein the surface of the calcium carbonate filler is coated with a silica inorganic coating layer.
The preparation method of the antibacterial polypropylene composite material of the embodiment 1 comprises the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, and the temperature of the fourth zone is 210 ℃.
Example 2
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 55% of copolymerized polypropylene, 5% of high-density polyethylene, 25% of kaolin filler, 5% of silver-doped nano zinc oxide, 3.5% of borane coupling agent, 5% of ethylene-butylene copolymer, 0.5% of antioxidant and 1% of ultraviolet absorbent; the surface of the kaolin filler is coated with a titanium dioxide inorganic coating.
The preparation method of the antibacterial polypropylene composite material of the embodiment 2 includes the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, and the temperature of the fourth zone is 210 ℃.
Example 3
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 75% of homo-polypropylene, 2% of high-density polyethylene, 10% of magnesium hydroxide filler, 2% of silver-doped nano zinc oxide, 3% of borane coupling agent, 7% of ethylene-butylene copolymer, 0.5% of antioxidant and 0.5% of ultraviolet absorbent; the surface of the magnesium hydroxide filler is coated with a silica inorganic coating layer.
The preparation method of the antibacterial polypropylene composite material of the embodiment 3 includes the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, and the temperature of the fourth zone is 210 ℃.
Comparative example 1
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 35% of homopolymerized polypropylene, 10% of high-density polyethylene, 30% of unmodified calcium carbonate filler, 8% of nano zinc oxide, 5% of borane coupling agent, 10% of ethylene-octene copolymer, 1% of antioxidant and 1% of ultraviolet absorbent.
The preparation method of the antibacterial polypropylene composite material of comparative example 1 comprises the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, and the temperature of the fourth zone is 210 ℃.
Comparative example 2
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 35% of homo-polypropylene, 10% of high-density polyethylene, 30% of unmodified calcium carbonate filler, 8% of nano zinc oxide, 5% of stearic acid surfactant, 10% of ethylene-octene copolymer, 1% of antioxidant and 1% of ultraviolet absorbent.
The preparation method of the antibacterial polypropylene composite material of comparative example 2 comprises the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, and the temperature of the fourth zone is 210 ℃.
Comparative example 3
The antibacterial polypropylene composite material comprises the following raw materials in percentage by mass: 35% of homo-polypropylene, 10% of high-density polyethylene, 30% of calcium carbonate filler, 8% of silver-doped nano zinc oxide, 5% of stearic acid surfactant, 10% of ethylene-octene copolymer, 1% of antioxidant and 1% of ultraviolet absorbent. Wherein the surface of the calcium carbonate filler is coated with a silica inorganic coating layer.
The preparation method of the antibacterial polypropylene composite material of the comparative example 3 comprises the following steps:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer for 1-3 times, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
The double-screw extruder is divided into four zones, wherein the temperature of the first zone is 190 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, and the temperature of the fourth zone is 210 ℃.
Mechanical Property test
The polypropylene composite materials prepared in examples 1-3 and comparative examples 1-3 were subjected to injection molding to obtain standard test specimens.
Tensile property: according to the test of GB/T1040-2006, the stretching speed is 50 mm/min; bending property, according to the test of GB/T9341-. The mechanical properties test results are shown in table 1.
TABLE 1 Performance test results for Polypropylene composites
As can be seen from Table 1, the polypropylene composites prepared in examples 1 to 3 of the present invention have higher strength and better toughness than those of comparative examples 1 to 3.
Test of antibacterial Property
The polypropylene composite materials prepared in the examples 1-3 and the comparative examples 1-3 are subjected to injection molding, a sample meeting the size requirement is prepared by referring to the national standard GB/T31402-2015, and the antibacterial performance of the polypropylene composite material samples prepared in the examples 1-3 and the comparative examples 1-3 is tested by a film pasting method. Counting colonies on the polypropylene composite samples of examples and comparative examples, respectively; the counting results showed that the number of colonies on the polypropylene composite samples of examples 1 to 3 was drastically reduced relative to the number of colonies on the polypropylene composite samples of comparative examples 1 to 3; through calculation, the antibacterial rate of the polypropylene composite material samples of the embodiments 1 to 3 can reach more than 98 percent; the polypropylene composite samples of comparative examples 1-3 had an antimicrobial rate of less than 70%. The antibacterial property test shows that the polypropylene composite materials of the embodiments 1 to 3 of the invention have excellent antibacterial property.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The antibacterial polypropylene composite material is characterized by comprising the following raw materials in percentage by mass: 35-90% of polypropylene, 0-10% of polyethylene, 5-30% of filler, 0.3-10% of doped nano zinc oxide, 0.2-5% of borane coupling agent, 0-10% of toughening agent and 0-2% of processing aid;
the filler is a modified filler prepared by a coating modification method, and the surface of the filler is coated with an inorganic coating layer;
the doped nano zinc oxide is silver-doped nano zinc oxide.
2. The antimicrobial polypropylene composite material according to claim 1, wherein the polypropylene is one of homo-polypropylene resin, co-polypropylene resin, or a mixture of homo-polypropylene resin and co-polypropylene resin.
3. The antimicrobial polypropylene composite of claim 1, wherein the polyethylene is one of high density polyethylene and low density polyethylene, or a mixture of high density polyethylene and low density polyethylene.
4. The composite material of claim 1, wherein the filler is one or a mixture of two or more of talc powder, calcium carbonate, barium sulfate, mica, wollastonite, kaolin, aluminum hydroxide and magnesium hydroxide.
5. The antibacterial polypropylene composite material of claim 1, wherein the inorganic coating layer on the surface of the filler is a silica coating layer or a titanium dioxide coating layer.
6. The antibacterial polypropylene composite material of claim 1, wherein the toughening agent is one or a combination of two or more of ethylene-octene copolymer, ethylene-butene copolymer and ethylene-propylene rubber.
7. The antibacterial polypropylene composite material as claimed in claim 1, wherein the doped nano zinc oxide is prepared by adding silver nitrate and a precipitant into a zinc salt solution, reacting, washing, drying and calcining at a high temperature.
8. The antimicrobial polypropylene composite material of claim 1, wherein the processing aid comprises one or a combination of two or more of antioxidants, lubricants, ultraviolet absorbers and heat stabilizers.
9. The method for preparing an antibacterial polypropylene composite material as claimed in any one of claims 1 to 8, comprising the steps of:
(1) weighing the raw materials according to the mass percentage, adding all the raw materials into a high-speed mixer, and fully and uniformly mixing;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melt kneading, extruding a mixed melt by the double-screw extruder after the kneading is finished, and cooling and then granulating to obtain the antibacterial polypropylene composite material.
10. The preparation method of the antibacterial polypropylene composite material as claimed in claim 9, wherein the twin-screw extruder is divided into four zones, the temperature of the first zone is 190-200 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 210-220 ℃, and the temperature of the fourth zone is 205-215 ℃.
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Application publication date: 20210608 |